Process for preparing liquid detergent



United States Patent 3,549,542 PROCESS FOR PREPARING LIQUID DETERGENT Victor M. Holderby, Cincinnati, Ohio, assignor to The Procter & Gamble Company, Cincinnati, Ohio, a corporation of Ohio N0 Drawing. Filed Oct. 2, 1967, Ser. No. 671,993 Int. Cl. Clld 1/38, 1/62, 1/65 US. Cl. 252-137 4 Claims ABSTRACT OF THE DISCLOSURE Liquid detergent compositions, especially shampoo compositions, generaly contain an anionic organic synthetic detergent as the principal ingredient. Cationic polymeric substances are desirably incorporated in such compositions for various purposes. For example, anionic organic detergent compositions containing various cationic polymeric substances are disclosed by Lang and McCune in US. Letters Patent 3,313,734, granted Apr. 11, 1967. The cationic polymers are employed in that patent to improve hair condition, i.e., wave set retention and hair manageability. Lang, US. patent application Ser. No. 586,013, filed Oct. 12, 1966, now Pat. No. 3,400,198, discloses anionic organic detergent compositions containing still other cationic polymers as hair conditioning additives.

Yet another invention which involves the use of a cationic polymer in an anionic organic detergent product is disclosed by Parren in US. application serial No. 476,175, filed July 30, 1965, now abandoned. The detergent compositions of the Parren invention contain cationic polymers to enhance deposition of and retention of particulate substances, e.g., antidandruff substances, on surfaces washed with the detergent.

Because of the well known incompatibility of anionic detergents and cationic polymeric substances, special measures must be taken to prepare stable homogeneous products containing these materials.

As taught in the forementioned disclosures, certain ampholytic and polar nonionic detergents serve to compatibilize cationic polymers and anionic detergents. However, such ancillary detergents are relatively expensive and manufacturing efficiency and quality control are unfavorably affected by complicating the formulation with these materials.

Apparently stable homogeneous liquid products containing both cationic polymers and anionic detergents can be prepared without such ancillary detergents by using high shear mixing techniques followed by milling in a colloid mill; however, such mixing can result in aeration of the product which ultimately leads to visible separation of product components. Until the present invention, processing measures per se had provided products containing substantial quantities of entrapped air.

It is an object of this invention to provide an improved method for preparing a liquid detergent composition containing an anionic detergent and a cationic polymer.

It is a further object of this invention to provide a method for preparing a nonaerated, stable, homogeneous liquid detergent composition containing a cationic polymer and an anionic detergent.

It is a still further object of this invention to provide 'ice a method for preparing a stable homogeneous liquid detergent composition containing a cationic polymer and an anionic detergent Without using ancillary ampholytic or polar nonionic detergents to compatibilize same.

These and other objects are accomplished by the invention hereinafter described and claimed.

In general terms, this invention comprises a process for preparing stable homogeneous liquid detergent compositions containing an anionic organic detergent and a cationic polymer comprising (1) mixing said polymer in an aqueous dispersion of a thickening substance selected from the group consisting of water-soluble cellulose derivatives and hydratable colloidal clays; (2) dispersing the resulting mixture in an aqueous solution of said detergent using low shear mixing means to prevent aeration; and (3) milling the resulting dispersion in a sealed colloid mill equipped with enclosed feed and discharge means.

It has been discovered that by mixing the cationic polymer with a cellulose derivative such as hydroxypropoxyl-substituted methyl cellulose or a colloidal clay such as a complex colloidal magnesium aluminum silicate, prior to its addition to the anionic detergent component, a surprisingly uniform dispersion of the polymer is obtained iwth only moderate agitation (low shear mixing). It is, of course, essential that the mixture be uniformly dispersed prior to milling in a colloid mill and this could heretofore be accomplished only by high shear mixing with attendant aeration.

Compositions prepared in accordance with the process of this invention contain, as hereinbefore stated, anionic organic detergents including both water-soluble soaps and nonsoap synthetic detergents. Operable nonsoap anionic organic detergents include, for example, water-soluble salts or organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 8 to about 20 carbon atoms and a radical selected from the group consisting of sulfuric acid ester and sulfonic acid radicals. Important examples of this type of nonsoap anionic synthetic detergent include the sodium or potassium alkyl sulfates, such as those derived by sulfation of higher alcohols produced by reduction of tallow or coconut oil glycerides; sodium or potassium alkylbenzene sulfonates, especially those of the types described by Guenther et al. in US. Pat. 2,220,099, granted Nov. 5, 1940, and by Lewis in US. Pat. 2,477,383, granted July 26, 1949, in which the alkyl group contains from about 9 to about 15 carbon atoms; sodium alkylglyceryl ether sulfonates, especially those ethers of higher alcohols obtained from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium salts of sulfuric acid esters of the reaction product of one mole of a higher fatty alcohol (i.e., tallow or coconut oil alcohols) and about 3 moles of ethylene oxide; and others well known in the art, a number being specifically set forth in Byerly, U.S. Pats. Nos. 2,486,921 and 2,486,922.

Additional nonsoap anionic organic synthetic detergents which can be used in this invention include the salts of the condensation products of fatty acids with sarcosine, i.e., acyl sarcosinate, wherein the acyl radical has a chain length range from about 10 to 18 carbon atoms. An especially preferred acyl sarcosinate for the purpose of this invention is sodium lauroyl sarcosinate.

Preferably, the nonsoap anionic organic detergent will be of the high sudsing type as for example, the alkylglycerylether sulfonates, the sulfated fatty alcohols or the alkyl ether ethylene oxide sulfates wherein the ethylene oxide chain averages 3 units, and acyl sarcosinates, all as more fully set forth above. These and the foregoing detergents can be used in the form of their sodium, potassium or lower alkanolamine such as triethanolamine salts.

Conventional soaps may also be used as the anionic detergent component of this invention. Suitable soaps include the sodium, potassium, and lower alkanolarnine salts of higher fatty acids of naturally occurring vegetable or animal fats and oils. For example, sodium, potassium and triethanolamine salts of fatty acids occurring in coconut oil, soybean oils, castor oil, tallow or synthetically produced fatty acids may be used.

If soap is to be used, it would desirably be used in small quantities, less than about and would be admixed with synthetic anionic detergents to form the anionic detergent component of the compositions of this invention. Preferably, the triethanolamine salt of coconut fatty acid would be used since it is more readily soluble than the salts of higher alkyl chain length fatty acids. Other preferred soaps include the sodium and potassium salts of coconut fatty acid.

Mixtures of any of the foregoing anionic detergents may also be used in the composition of this invention.

The anionic organic detergent can be employed in concentrations ranging from about 4.0% to about 30.0% by weight of the total composition with the preferred range being from about 7% to about Because of the excellent solubility and lathering properties of anionic nonsoap detergents containing predominantly C and C alkyl chain lengths and their ready availability, these are preferred for the purpose of this invention.

The cationic polymers which can be incorporated in detergent compositions through the practice of this invention include water-soluble polymers at least mole percent of the molecular structure of which are composed of monomeric units containing one or more quaternary ammonium groups and any balances of which are comprised of nonquaternized polymeric uits derived from monoethylenically unsaturated groups. Such polymers include, for example, quaternized polyvinylimidazole, quaternized poly(dimethylaminoethylmethacrylate), quaternized poly- (p-dimethylaminomethylstyrene) and others disclosed in U.S. Pat. 3,313,734 having molecular weights of from about 1,000 to about 5,000,000.

Yet other cationic polymers are those disclosed by Parran in U.S. application Ser. No. 476,175, filed July 30, 1965, i.e., polyethylenimine or alkoxylated polyethylenimine having a molecular weight greater than about 100 but less than about 500,000.

Still other cationic polymers which can be added to anionic detergents by the process of this invention are (1) the water-soluble quaternary nitrogen-substituted cellulose derivatives available under the code designation JR-lL; (2) the water-soluble linear polyamines available under the trade name Primafloc, and related polymers disclosed in U.S. Letters Pat. 3,300,406, granted Jan. 24, 1967; (3) the water-soluble polymers of epichlorohydrin and tetraethylene pentamine available under its trade name Nalco 600. All of these latter polymers are watersoluble cationic tertiary amine or quaternary ammoniumcontaining polymers having molecular weights within the range from about 2,000 to 3,000,000, and having a cati onic charge density 6 number of positive charges unit molecular weight greater than about 0.001.

It can be seen that the present invention finds application in connection with the addition of any cationic polymer to any anionic organic detergent in a liquid form. Thus, the specific nature of the involved cationic polymer is not critical. Rather, it is the inherent incompatibility of cationic materials generally with anionic detergents that renders the present invention useful in its broadest aspect.

The cationic polymer can be incorporated in detergent compositions of the type herein contemplated at concen trations ranging from about 0.1% to about 7.0% by weight. The optimum concentration Will vary depending on the type of polymer employed and its intended purpose in the composition. Detergent compositions containing more than about 7.0% of cationic polymer are difficult to formulate without high shear mixing and concomitant aeration of the product. Concentrations of cationic polymer less than about 0.1% do not generally provide the desired effect in the composition.

One of the alternative groups of thickening materials which can be admixed with the cationic polymer prior to incorporating same in the anionic detergent to obtain the benefits of this invention are the cellulose derivatives. The cellulose derivatives effectively increase the viscosity of liquid products to desired levels while at the same time serving the purpose of this invention. The preferred cellulose derivatives are the water-soluble cellulose ethers, including methylcellulose, ethylcellulose, hydroxyethylcellulose, carboxymethylcellulose (especially sodium carboxymethylcellulose), carboxyethylcellulose, sulfoethylcellu lose, and sodium cellulose sufates. Sodium carboxymethylcellulose, hydroxyethylcellulose and hydroxypropoxylsubstituted methylcellulose ethers, are especially preferred cellulose derivatives for the purpose of this invention.

Carboxymethylcellulose is made by treating alkali cellulose with sodium chloroacetate until the desired degree of substitution (.D.S.-the average number of hydroxyl positions on the anhydroglucose unit that have been etheritied) has been reached. Preferably, the sodium carboxymethylcellulose employed herein will have approximately two etherified hydroxyl groups for every anhydroglucose unit. This material and a complete description of its preparation are disclosed by Waldeck in U.S. Letters Patent 2,510,355. 'It is readily available on a commercial scale from a number of sources and in varying grades. It is used in the present invention in the form of a white free-flowing powder that quickly dissolves in water.

Hydroxyethylcellulose is, of course, comprised of hydroxyethyl-substituted anhydroglucose units. This material is prepared by reacting alkaline cellulose with ethylene oxide as is more fully described by Gloor et al., Ind. Eng- Chem., 42:2150 (1950). The degrees of subscription is preferably about 1.0 to assure good water solubility. This cellulose derivative is also manufactured on a commercial scale and is readily available from a number of sources. It too is used as a white free-flowing powder which readily disperses and dissolves in water.

The hydroxypropoxyl-substituted methylcellulose ethers contain varying ratios of hydroxypropoxyl to methoxyl substituents on the anhydroglucose units. Suitable cellulose derivatives of this group contain from about 19% to about 30% by weight of hydroxypropoxyl substituents on the anhydroglucose units. The degree of substitution with methoxyl and hydroxypropoxyl groups can vary from about 1.08 to 1.82 and from about .07 to 0.3, respectively. The molecular weight of these materials range from about 100,000 to about 175,000. These products are commercially available from the Dow Chemical Company and are sold under the trade name Methocel.

The preferred hydroxypropoxyl-substituted methylcellulose is comprised of from 28% to 30% by weight of methoxyl substituents and from 7% to 12% by weight of hydroxypropoxyl substituents. The degree of substitution with methoxy and hydroxypropoxyl substituents is from about 1.68 to 1.82 and from 0.17 to 0.3, respectively.

Cellulose derivatives can be used in detergent compositions at concentrations ranging from about 0.1% to about 5.0% by Weight. Preferably, it will comprise from about 0.2% to about 1.0% by weight of the total composition.

The second class of alternative components which can be premixed with the cationic polymer prior to incorporating same in detergent compostions in accordance with this invention are the hydratable colloidal clays, such as montmorillonites, sodium bentonites, hcctorites and the complex colloidal magnesium aluminum silicates, as well as mixtures of these clays.

Montmorillonite, a clay-mineral which is hydrous aluminum silicate with a silicon-to-metallic oxide ratio equal to about four, is characterized by an expanding lattice, structure.

Bentonite, a native, colloidal hydrated aluminum silicate, is comprised of about 90 percent montmorillonite. A typical sodium bentonite is comprised as follows:

Component: Percent by weight Silicon dioxide (S102) 64.32 Aluminum oxide (A1 20.74 Ferric oxide (Fe O 3.03 Ferrous oxide (FeO) 0.46 Titanium dioxide (TiO 0.14 Phosphoric acid 0.01 Calcium oxide (CaO) 0.52 Magnesium oxide (MgO) 2.30 Sodium oxide (Na O) 2.59 Potassium oxide (K 0) 0.39 Sulfur (S0 0.35 Minors 0.01 Bound water 5.14

This material is a fine, odorless, cream-colored powder which is insoluble in water but which swells to approximately twelve times its volume when added to water.

Hectorite is also a member of the montmorillonite clays. The major ditferentce between hectorite and bentonite is the almost complete substitution of aluminum in the lattice structure of bentonite by magnesium in hectorite and the presence of lithium and fluorine in the lattice structure of hectorite.

The complex colloidal magnesium aluminum silicates are commercially available under the trademark Veegum. This material is derived from montmorillonite and hectorite and is supplied in the form of odorless, tasteless, -white flakes. An average chemical analysis of complex colloidal magnesium aluminum silicates is as follows:

Component: Percent by weight Silicon dioxide (SiC 61.1 Magnesium oxide (MgO) 13.7 Aluminum oxide (A1 0) 9.3 Titanium dioxide (TiO 0.1 Ferric oxide (Fe O 0.9 Calcium oxide (CaO) 2.7 Sodium oxide (Na O) 2.9 Potassium oxide (K 0) 0.3 Carbon dioxide (CO 1.8 Bound water 7.2

The foregoing clays can be used alone or in combination with one or more of the cellulose derivatives hereinbefore described to provide the desired viscosity to the liquid detergent products. In accordance with this invention these same materials can be used, alone or in combination, as a premix for cationic polymers to provide uniform dispersion in the anionic detergent component.

The colloidal clays can be used in this invention in concentrations ranging from about 0.1% to about 5.0%. Preferably, this component will comprise from about 0.8% to about 1.3% of the total composition.

The total concentration of thickener can range from about 0.1% to about 7.0% if mixtures of a cellulose derivative and a colloidal clay are to be used to thicken the detergent composition. It is to be understood that the cationic polymer can be premixed with either the cellulose derivative or the colloidal clay if a combination of these components is used. Alternatively, a portion of the cationic polymer can be premixed in both of these components.

Various minor ingredients can be added to compositions prepared in accordance with the process of this invention, including dyes, antimicrobial agents, perfumes, opacifiers, and sequestering agents. Water will in any event comprise the balance of the composition.

In the preparation of a liquid detergent by the method of this invention, an aqueous solution of the cationic polymer is prepared having a concentration within the range from about 1.0% to about 35.0% by weight, preferably about To the cationic polymer solution is then added the powdered cellulose derivative and/or c01- loidal clay and the mixture is agitated until hydration is essentially complete. Alternatively, the cellulose derivative or colloidal clay can be dispersed in water and the cationic polymer can then be added to the hydrated cellulose derivative or colloidal clay. In either event, the resulting premix of polymer and thickener will preferably contain from about 2% to about 10%, more preferably from 4% to 6% by weight of thickener. The premix is then dispersed in an aqueous solution of the anionic detergent, preferably at a concentration within the range from about 4.0% to about 60.0%, using low shear agitation. Other desired ingredients are also added to the main mix at this time, including an amount of water sufficient to provide the desired concentration of ingredients in the final product. The resulting dispersion is then milled in a closed system colloid mill. The resulting product is a stable homogeneous liquid detergent composition.

Although the temperatures of the polymer/thickener premix and anionic detergent-containing main mix are not critical, the cationic polymer solution will preferably be maintained in the range of from about 40 F. to about 200 F. when added to the thickener. The anionic detergent component in the main mix is preferably heated to a temperature within the range from about F. to about F. prior to the addition of the cationic polymer/thickener premix.

The terms low shear mixing and low shear agitation are used interchangeably herein and refer to the means and/or methods for dispersing the ingredients of the involved compositions which do not aerate the compositions to any substantial degree. Any of the well known commercial propeller or turbine type agitators can be used if operated at speeds or adjustments which do not lead to the entrapment of air bubbles.

The closed system colloid mill specified for use in the present process is available in a variety of designs from a number of manufacturers. The terms closed system and sealed used herein to characterize such mills refers to airtight inlet and discharge means which preclude the introduction of atmospheric air during the milling procedure. A general discussion of colloid mills and other mixing means is found in Sagarin, Cosmetics Science & Technology, pages 1020-1022 (Interscience Publishers, Inc., 1957).

The process of this invention is fully illustrated by reference to the following examples which are not to be construed as limiting the invention in any way.

EXAMPLE I A liquid detergent formulation of the following composition was prepared using the process of this invention.

Component: Percent by weight Triethanolamine coconut 1 sulfate 20.00 Triethanolamine 1.60 Zinc 2-pyridinethiol-l-oxide 1.00 Polyethylenimine/ ethylene oxide r e a c ti o 11 product 2 1.00 Hydroxypropoxyl substituted methyl cellulose 3 0.24 Coconut 1 monoethanolamide 4.00 Veegum 4 0.95 Coloring 0.10 Perfume 0.25 Distilled water Balance 1 The term coconut as used herein refers to alkyl groups which are derived from the middle-cut of coconut alcohol having the followin approximate chain length distribution: 2%-C1o; 66% m; 23%C14; and 9%C1e.

Polyethylenimine having a molecular Weight of 40,000 to 60,000; weight ratio of polyethylenirnine to ethylene oxide equals 1 :1; and total molecular weight 80,000 to 120,000.

3 Methocel 60 HG comprised of from 28% to 30% by weight of methoxyl and from 7% to 12% by weight of hydroxypropoxyl substltuents. Degree of substitution with rnethoxy and hydroxypropoxyl substituents is 1.68 to 1.82 and from 0.17 to 0.3, respectively.

4 Complex colloidal magnesium aluminum silicate as defined supra.

The above composition was prepared as follows: 4.8 grams of the hydroxypropoxyl-substituted methyl cellulose were added to 60 to 120 grams of water heated to 180- 200 F. in a 250 ml. beaker. The mixture was agitated with an air-operated two-bladed propeller-type stirrer for 15 minutes to provide a smooth dispersion. To this dispersion was added 50 grams of a 40% aqueous solution of the ethoxylated polyethylenimine and agitation was continued until the mixture was smooth.

The above premix was added to a steam-jacketed 3,000-gram cylindrical stainless steel main mix tank equipped with a Lightnin mixer having a 2"-diarneter turbine and operating at approximately 50 r.p.m., containing a mixture of 1111.2 grams of a 36% aqueous solution of the triethanolamine coconut sulfate, 32 grams of triethanolamine and 40.0 grams of a 50% aqueous dispersion of the zinc Z-pyridinethiol-l-oxide, all heated to 160-190 F. Low shear mixing was continued while 80 grams of coconut monoethanolamide were melted into this main mix, followed by the addition of 2.0 grams of coloring material.

361.0 grams of water were then heated to 180-210 F. and 19.0 grams of the Veegum were slowly added thereto with agitation. The Veegum was allowed to hydrate for one hour and was then added to the mixture in the main mix tank.

Perfume and the balance of the water were added to the main mix tank and the entire mixture was agitated using the above-described low shear mixing means of the main mix tank for 15 minutes. The ingredients at this point were either in solution or uniformly dispersed and the mixture was essentially nonaerated. The mixture was then milled at .002 inch gap in a Gaulin colloid mill having sealed feed and discharge ports to prevent the introduction of atmospheric air during the milling operation.

A stable homogeneous liquid detergent composition, essentially free of entrapped air, resulted from the foregoing process.

EXAMPLE II A product identical in formulation to that specified in Example I was prepared in accordance with the process of the invention on a larger scale than in Example I as follows:

To 2.50 lbs. of a 40% aqueous solution of the ethoxylated polyethylenimine dissolved in 2 to 6 lbs. of Water were slowly added 0.24 lb. of the hydroxypropoxyl-substituted methyl cellulose in a stainless steel pot, in diameter and 8 in depth. A Lightnin mixer with a 2"-diameter turbine mounted in the pot was operated at a speed sufiicient to provide a vortex reaching approximately half the length of the pot. This mixture was heated to 170190 F. and mixing, as described, was continued for minutes.

The polymer/ cellulose derivative premix prepared as above was then added to the main mix tank consisting of a steam-jacketed stainless steel tank of 250 lbs. capacity, having a conical bottom and equipped with a six'bladed turbine 10" in diameter with blade pitch angles of 45, containing a mixture of 55.56 lbs. of a 36% solution of triethanolamine coconut sulfate, 1.60 lbs. of triethanolamine and 2.0 lbs. of a 50% aqueous dispersion of Zinc Z-pyridinethiol-l-oxide, heated to about 160190 F. These ingredients were then mixed using low shear mixing r.p.m.) while 4.0 lbs. of coconut monoethanolamide were melted into the main mix tank, followed by the addition of 0.1 lb. of coloring.

18.05 lbs. of water were then heated to 180210 F. and 0.95 lb. of Veegum were slowly added thereto in a 10-gallon Hubbert steam-jacketed stainless steel kettle equipped with a scraped-wall low-speed agitator, and a high-speed 2" turbine located at the bottom of the kettle. The low shear mixing continued for about one hour after which the hydrated Veegum was added to the main mix tank.

The perfume and the balance of the water were added to the main mix tank where the entire mixture was mixed at 20 r.p.m. for 15 minutes. The uniform disperson of these ingredients thus provided was milled at 0.002 inch gap in a 3 Tri-Homo colloid mill having a sealed feed and discharge port.

The resulting product was a homogeneous liquid, essentially free of entrapped air. The product remained stable throughout three months of storage at temperatures of 50 F., F., F., and F.

EXAMPLE III Formulations identical to those prepared in Examples I and II but containing triethanolamine dodecylbenzene sulfonate, potassium coconut glyceryl ether sulfonate and the sodium and ammonium salts of the sulfated condensation product of 1 mole of coconut fatty alcohols and 3 moles of ethylene oxide, respectively, in place of triethanolamine coconut sulfate, are formulated in accordance with the process of Example I. The resulting products are stable homogeneous liquids essentially free of entrapped air.

EXAMPLE IV A composition of the formulation set forth in Example I was prepared in the following manner:

1111.2 grams of triethanolammonium coconut sulfate, 32.0 grams of triethanolamine, and 40.0 grams of a 50% aqueous suspension of zinc Z-pyridinethiol-l-oxide were placed in a 3,000-gram steam-jacketed stainless steel main mix tank and were heated to -190 F.

4.8 grams of hydroxypropoxyl-substituted methyl cellulose was added to 3 to 6 parts of water heated to 200 F. and agitated for 15 minutes to provide a smooth dispersion. The hydrated dispersion was then added to the main mix tank.

80 grams of coconut monoethanolamide was added to the main mix tank and allowed to melt; after melting, this ingredient was thoroughly mixed with the other ingredients using low shear mixing to prevent aeration. 2.0 grams of coloring was also added and mixed with the other ingredients at this point in the process.

50 grams of a 40% aqueous solution of the ethoxylated polyethylenimine was diluted with 311 grams of water and heated to 180210 F. in a Waring Blendor adjusted to provide a vortex to the bottom of the chamber. 19.0

grams of Veegum was slowly added to the polymer solution and allowed to hydrate for one hour with agitation. The polymer/hydrated Veegum dispersion was then added to the main mix tank at a temperature about 40 F.

The perfume and other minor ingredients were added to the main mix tank and the batch was mixed for 15 minutes. The complete mixture was then milled at .002 16031 Pin a closed system Gaulin colloid mill and cooled to The resulting liquid detergent composition was a stable homogeneous product essentially free of entrapped air.

EXAMPLE V Additional compositions are prepared in accordance with the procedure of Example IV but using a substantially completely quaternized polyvinylimidazole, having a molecular weight of about 100,000; dimethyl sulfate quaternized poly(diethylaminoethylmethacrylate) having a molecular weight of about 500,000 and prepared in accordance with Example I of U.S. 2,723,256 granted Nov. 8, 1955; substantially completely quarternized poly (p-dimethylaminomethylstyrene) having a molecular weight of approximately 250,000; substantially completely methyl phosphate quaternized poly(dimethylaminoethyl methacrylate) having a molecular weight of about 5,000; JR1L as hereinbefore described; Nalco 600 as hereinbefore described; Primafloc as hereinbefore described; and a water-soluble polyethylenimine having an average molecular weight of about 100,000 and a viscosity of 2.5 centipoises in a 1% by weight aqueous solution; respectively, in place of the ethoxylated polyethylenimine. The resulting products are stable, homogeneous liquids which are relatively nonaerated.

EXAMPLE VI Liquid detergent compositions are formulated as in Example I using the process of that example but substituting methyl cellulose, ethyl cellulose, carboxymethylcellulose, sodium carboxyethylcellulose, hydroxyethylcellulose, sulfoethylcellulose, and sodium cellulose sulfate, respectively, for the hydroxypropoxyl-substituted methyl cellulose, with substantially equivalent results.

EXAMPLE VII Formulations of Example I are prepared in accordance with the process of Example IV but substituting a montmorillonite, sodium bentonite and hectorite clay, respectively, for Veegum with substantially equivalent results.

Unless otherwise specified, the percentage values employed herein refer to percent by weight.

Although the formulations set forth herein in the examples include a number of ancillary ingredients, it is to be understood that the process described and claimed herein is useful in the preparation of stable homogeneous liquid detergents containing any desired organic anionic detergent and cationic polymer without regard to other ingredients.

What is claimed is:

1. A method for preparing a stable, homogeneous liquid detergent composition consisting essentially of (a) a cationic polymer selected from the group consisting of polyethylenimine, the reaction product of ethylene oxide and polyethylenimine, quaternized polyvinylimidazole, quaternized poly(diethylaminoethylmethacrylate), quaternized poly (ldimethylaminoethylmethacrylate), and quaternized poly(p-dimethylaminomethylstyrene), said polyethylenimine and alkoxylated polyethylenimine having a molecular weight greater than 100, but less than 500,000 and said quaternized compounds having a molecular weight of from about 1,000 to 5,000,000 and (b) an anionic organic detergent, comprising the steps of: (1) preparing an aqueous mixture of from about 1% to about 35% by weight of said cationic polymer, and from about 2% to about by weight of a thickening substance selected from the group consisting of hydratable colloidal clays and watersoluble cellulose derivatives selected from the group consisting of hydroxylpropoxyl-substituted methyl cellulose, sodium carboxymethylcellulose, methylcellulose, ethylcellulose, hydroxyethylcellulose, sulfoethylcellulose, and sodium cellulose sulfate; (2) dispersing the resulting mixture in an aqueous solution of said anionic organic detergent at a concentration within the range of from about 4% to about by weight and at a temperature within the range of from about F. to about B, using low shear mixing means to prevent aeration; and (3) milling the resulting dispersion in a sealed colloid mill having enclosed feed and discharge means.

2. A method in accordance with claim 1 wherein the anionic detergent is a fater-soluble salt of a member selected from the group consisting of higher fatty acids, anionic organic sulfuric reaction products having in their molecular structure an alkyl containing from about 8 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group, and acyl sarcosinates wherein the acyl group contains from about 10 to about 18 carbon atoms.

3. A method in accordance with claim 1 wherein the thickening substance is a hydratable colloidal clay selected from the group consisting of complex colloidal magnesium aluminum silicates, montmorillonite, sodium bentonite, and hectorite clays.

4. A method in accordance with claim 2 wherein thickening substance is a hydratable colloidal clay selected from the group consisting of complex colloidal magnesium aluminum silicates, montmorillonite, sodium bentonite, and hectorite clays.

References Cited UNITED STATES PATENTS 2,914,482 11/1959 Kopp 252-152 3,150,098 9/1964 Wilson 252152 M. HALPERN, Assistant Examiner LEON D. ROSDAL, Primary Examiner US. Cl. X.R. 252152 Po-wso Patent No.

Dated December 22, 1970 Victor M. Holderby It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column line 24,

, line line , llne a, line 66,

10, line 2,

1o, linel6,

Signed and (SEAL) Attest:

EDWARD M.PLETCHER,JR. Attesting Officer "iwth" should read -with "or" should read --of.

"uits" should read -units-.

"dif ferentce" should read --difference--.

"quarternized" should read -quaternized- "watersoluble" should read -water-solubl "fater-soluble" should read -watersolu' sealed this 11th day of May 1971 WILLIAM E. SCHUYLER, JR. Commissioner of Patents 

